TW201120073A - Production method for modified conjugated diene polymer, modified conjugated diene polymer, and modified conjugated diene polymer composition - Google Patents

Abstract

Disclosed is a modified conjugated diene polymer and a modified conjugated diene polymer composition which yield a vulcanizate exhibiting excellent processability, an excellent balance between wet skid resistance and low hysteresis loss, and having a wear resistance and a breaking strength sufficient for practical use. The method for producing a modified conjugated diene polymer comprises a polymerization step, in which a conjugated diene polymer having an active terminal is obtained by using an alkali metal compound or an alkaline earth metal compound as a polymerization initiator to polymerize a conjugated diene compound or copolymerize a conjugated diene compound and an aromatic vinyl compound; and a modification step, in which a compound having a specific structure is reacted with the active terminal of the conjugated diene polymer.

Description

201120073 VI. [Technical Field] The present invention relates to a method for producing a modified conjugated diene polymer, a modified conjugated diene polymer, and a modified conjugated diene polymerization. Composition 0 [Prior Art] In recent years, environmental considerations such as suppression of carbon dioxide emissions are becoming a requirement for punctuality. Specifically, the question of the low fuel consumption of automobiles has gradually been asked. In view of such a situation, it is required to develop a material having a small rotational resistance as a material for a tire for an automobile, particularly a tire surface in contact with the ground. On the other hand, from the viewpoint of safety, it is required to develop a material which is excellent in wet skid resistance and has practically sufficient abrasion resistance and fracture characteristics. It is not used as a reinforcing filler for the tread surface. 73⁄4 7U 1 尔 13⁄4 with black, 备 矽, etc. From the age of ..., - milk, /, with the right to use cerium oxide, can achieve the advantages of low hysteresis loss and improved. However, the dioxotomy of the water-repellent surface of the carbon yarn with respect to the hydrophobic surface has the disadvantage of being inferior to the m-type rubber or the dispersibility compared with the ruthenium black, and therefore, in order to improve the dispersion Γ ί 二 二 二 二 二The bond between the oaks must be additionally contained in the Shixiyuan rubber. Two: Years: The following attempts were made: by virtue of the higher mobility, the introduction of affinity or reactivity with cerium oxide is good: The dispersibility of the dioxide in the rubber material, and then the end of the rubber molecule is blocked by the bonding of the Shixi particles, and the low hysteresis loss is reduced by 150826.doc 201120073. For example, Patent Document 1 discloses a modified diene rubber obtained by reacting a modifier having a glycidylamino group with a polymer terminal, and Patent Document 2 discloses that glycidyloxyalkylene is disclosed. A modified diene rubber obtained by reacting oxydecane with a polymer terminal. Further, Patent Documents 3 to 7 disclose modified diene rubber obtained by reacting an alkoxy decane having an amino group with a polymer terminal, and a combination thereof with cerium oxide. [PRIOR ART DOCUMENT] [Patent Document 1] International Publication No. 01/23467 pamphlet [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei 7-233217 (Patent Document 3) Patent Application No. 2〇01_158834 [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 7/34785 [Patent Document 5] International Publication No. 8/13〇9〇 Brochure [Patents] Document 7] International Publication No. 7/1142〇3 Booklet [Summary of the Invention] Problems to be Solved by L Invention] However, when a functional group having a high reactivity of ruthenium-prepared ruthenium oxide is introduced into the terminal At the time of the kneading step, the robe # is two, /Mi Ningjin and the cerium oxide particles react, and the viscosity of the composition rises, and the tendency of deterioration of the following processing properties such as the following may occur. After the mixing, the point y is apt to form a sheet which is prone to surface roughness or cracking. In addition, when vulcanized rubber is produced, ^^, ., when making a vulcanized rubber containing an inorganic filler, it is required to further improve the low hysteresis loss and the wet skid resistance. The present invention is directed to the above-mentioned circumstances, and an object of the present invention is to provide a modified oxime: a method for producing an olefinic polymer, a diterpene-based polymer, and a modified conjugated diene-based polymer composition. When the modified conjugated diene polymer is used as a vulcanized rubber, it has excellent balance between low hysteresis loss and wet skid resistance, and has practically sufficient abrasion resistance and fracture strength, and is excellent in workability. [Means for Solving the Problems] The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by the following method for producing a modified conjugated diene polymer, which comprises the following steps a polymerization step of using an alkali metal compound or an alkaline earth metal compound as a polymerization initiator to combine or copolymerize a conjugated diene compound or a conjugated diene compound with an aromatic vinyl compound I, thereby obtaining an active terminal A total of two dilute polymer 'and a upgrading step' which reacts a compound of a specific structure with the above-mentioned active terminal of the above-mentioned co-diuretic polymer; thereby completing the present invention. The invention is as follows. [1] A method for producing a modified conjugated diene polymer, comprising the step of polymerizing an conjugated diene compound or a conjugated diene using an alkali metal compound or an alkaline earth metal compound as a polymerization initiator Polymerizing or copolymerizing a compound with an aromatic vinyl compound, thereby obtaining a conjugated diene polymer having an active terminal; and s 150826.doc 201120073 a upgrading step of polymerizing a modifier with the above conjugated diene The above-mentioned active terminal reaction of the substance has a heterocyclic structure containing two or more nitrogen atoms and a hydrocarbon, and two or more decanes having two or more alkoxy groups bonded thereto Base compound. [2] The method for producing a modified conjugated diene polymer according to [1], wherein the modifying agent is a compound represented by the following formula (1): [Chemical Formula 1] (R 0)-Si-R -—N m I R3 K (3-m)

(1) (In the formula (1), R to R are each independently, and represent a carbon group or an aryl group of the carbon number (9), and R5 and R6 are each independently, and represent a carbon number of "alkyl", and R7 and R8 are independent, respectively. A hydrocarbon group having 1 to 6 carbon atoms, and adjacent to each other form a ring structure of 5 or more rings, and the claws and 11 are independent, respectively, representing an integer of 2 or 3.) [3] A total of 改] or [2] The method for producing a conjugated diene polymer, wherein all of the above-mentioned calcined groups are bonded to a group of three methoxy groups. [4] As in any one of [1] to [3] The method for producing a modified conjugated diene polymer, wherein the total mole number of the methoxy group bonded to the dream base in the modifier is added to the molar amount of the polymerization initiator 150826.doc 201120073 [5] The method for producing a modified light diuretic polymer according to the item H to [4], wherein the polymerization step is continuous. [6] (1) to [5] In the middle of the term - the change of the f-light two-material polymer manufacturer's two '::" the use of the total L-woman polymer by gel permeation chromatography (10) 〇 (4) styrene-converted number average molecular weight is ,coffee~ 600500〇 7 [7] A modified di-based polymer obtained by the method for producing a modified conjugated diene polymer according to any one of [1] to [6]. [8] A modified conjugated diene polymer composition comprising: 100 parts by mass or more of a rubber component containing 20 parts by mass or more of the modified conjugated diene polymer as described in [7], and dioxide矽-based inorganic filler 0 5~3 〇〇 parts by mass. [Effects of the Invention] According to the present invention, a method for producing a modified conjugated diene polymer, a modified conjugated diene polymer, and a modified conjugated diene polymer group S can be provided. When the modified conjugated diene polymer is used as a vulcanized rubber, it has excellent balance between low hysteresis loss and wet skid resistance, and has practically sufficient abrasion resistance and fracture strength, and is excellent in workability. [Embodiment] Hereinafter, the present embodiment for describing the present invention (hereinafter referred to as "--------" However, it is not intended to limit the invention to the following. The present invention can be suitably modified and implemented within the scope of the gist of the invention. The method for producing a modified conjugated diene polymer of the present embodiment includes the following steps: a polymerization step of using an alkali metal compound or an alkaline earth metal compound as a polymerization initiator to make a co-diene compound or a conjugated diene compound Polymerizing or copolymerizing with an aromatic vinyl compound, thereby obtaining a co-lighter system polymer having an active terminal; and a upgrading step of reacting the modifying agent with the above-mentioned active terminal of the above conjugated diene polymer The modifier is a compound having one or more heterocyclic rings containing two or more nitrogen atoms and a hydrocarbon, and having two or more alkylene groups in which two or more alkoxy groups are bonded. In the polymerization step of the modified common diene polymer of the present embodiment, a metal test compound or a soil test metal compound is used as a polymerization initiator': a dilute compound or a co-battery compound and aromatic vinyl The base compound is poly- or copolymerized, whereby a conjugated diene polymer having a right-handed, lingual end is obtained. = copolymerization of a copolymer of a copolymer of a diene polymer, a polymer of a single conjugated olefin compound, or a copolymer of a conjugated diene compound of a total of two conjugated diene compounds Things. The round-back compound and the aromatic vinylated isoamyl, 2,3-didecyl=co-dry dilute compound can be a monomer capable of polymerization, and there is no particular limitation, for example, 1,3. 150826*doc 201120073 Butadiene, 1'3-decadiene, 3-methyl], 3-pentadiene, 丄3•geng Erfu, U3-hexadiene, etc. Among these, it is industrially easy to obtain: From the viewpoint, it is preferable to be butadiene or isoprene. These may be used singly or in combination of two or more. The aromatic B compound is not particularly limited as long as it can be polymerized with the common light, and examples thereof include, for example, stupid ethylene, stilbene, and α-methyl styrene. , vinyl ethyl benzene, ethylene dimethyl strepene naphthalene, diphenyl ethylene and the like. Among these, from the viewpoint of ease of industrial availability, styrene is preferred. These may be used singly or in combination of two or more. In the case where the common dibasic polymer is a copolymer, it may be a random copolymer or a block copolymer. Examples of the random copolymer include butadiene-isoprene random copolymer, tauadiene stupid ethylene random copolymer, isoprene styrene random copolymer, and butyl U pentane Benzene random copolymer and the like. The composition distribution of each monomer in the copolymer chain may, for example, be a completely random copolymer which is statistically close to a random composition or a tapered random copolymer having a distribution of a composition having a tapered shape. The composition of the common two-dense bonding method, I7, bond, α, or 1,2-bonding may be uniform or distributed. Examples of the daddy copolymer include a type 3 block copolymer comprising two block type 2 block copolymers of 33 3 groups, and a type 4 embedded body containing four blocks. For example, '8' indicates an aromatic vinylated block such as styrene, and a block containing a conjugated monoolefin compound such as butyl dipentide or isoprene, and/or aromatic vinyl group. The block of the copolymer of the base compound and the conjugated monoalkylene oxide is an S-B2 type block copolymer, S-150826.doc £201120073 B-S3 type block copolymer, SBS-B4 type block Copolymer and the like are indicated. In —t, the boundaries of the blocks do not need to be clearly distinguished. In the case where the block B is a copolymer of an aromatic alkenyl compound and a conjugated diene compound, the aromatic vinyl compound in the embedding B may be uniformly distributed or may be distributed in a conical manner. Further, in the block B, a portion in which a plurality of aromatic vinyl compounds are uniformly distributed and/or a portion in which the pyramid is distributed may be coexisted. Further, in the block B, a plurality of fragments having different contents of the aromatic vinyl compound may be coexisted. When a plurality of blocks s and blocks B are present in the copolymer, the structures such as the molecular weight or the composition may be the same or different. In the present embodiment, all or a part of the double bond can be converted into a saturated hydrocarbon by hydrogenating the conjugated diene polymer having a functional group in an inert solvent. In this case, heat resistance and weather resistance are improved, and deterioration of the product at the time of processing at a temperature can be prevented. As a result, it is used in various applications such as automobiles: it exhibits superior performance on the way. More specifically, the hydrogenation of the unsaturated double bond based on the conjugated diene compound (i.e., "hydrogenation rate") can be arbitrarily selected depending on the purpose, and is not particularly limited. When it is used as a vulcanized rubber, it is preferably a double bond remaining portion of the conjugated diene portion. From this point of view, the hydrogenation rate of the common dilute portion in the polymer is preferably from 3 to 70 Å. More preferably, it is 5 to 65%, and further preferably 10 to 60%. Further, the hydrogenation rate of the aromatic (tetra) double bond of the aromatic ethylenic compound in the copolymer of the conjugated diene compound and the aromatic vinyl compound is not particularly limited, but is preferably 5% or less, more preferably 30. /. Hereinafter, it is more preferably 20% or less. The hydrogenation rate can be measured by a nuclear magnetic resonance apparatus. 150826.doc -10- 201120073 The hydrogenation method is not particularly limited, and a known method can be used as a particularly suitable hydrogenation method, and a method of blowing gaseous nitrogen into the solution of the catalyst in the presence of a catalyst may be mentioned. The method of transformation. For the medium, it can be mentioned that the precious metal is supported on the porous inorganic substance, and the contact catalyst is used as a catalyst, and the catalyst is mixed with the organic salt. Catalysts such as titanium and other metallocenes are all media. Among these, in particular, it is possible to select a mild gasification condition. The hydrogenation of the aromatic group can be carried out by using a supported catalyst of a beryllium metal. As a specific example of the hydrogenation catalyst, (1) Ni, and other metals are supported on carbon, sulphur dioxide, sulphuric acid, and shisha algae-type chlorinated catalyst, and (7) , co, Fe, cr#: t= = so-called Ziegler-type chloride catalysts such as transition metal salts such as propyl-salt and organic reducing agents, and (3) organometallic A-forms such as Ti and Rnzr Specialized in so-called organic metal complexes. For example, as a chlorination catalyst, Japanese Patent Publication No. Sho 42. No. 4, Japanese Patent Publication No. Sho. No. 6636, Japanese Patent Special Public Promo, No. W-7970, Japanese Patent Application No. The hydrogenation catalyst described in the Japanese Patent Publication No. Hei. No. Hei. As a preferred hydrogenation catalyst, a reaction mixture of a titanocene compound and a reducing organometallic compound can be mentioned. The metal compound used as the polymerization initiator is not particularly limited, and is preferably an organic clock compound. Examples of the organic clock compound include a low molecular compound, an organic lithium compound which is a soluble polymer, a compound containing a carbon-lithium bond in an organic group and lithium, and a nitrogen-lithium bond. a compound, a compound containing a tin-lithium bond, or the like. Examples of the organolithium compound include n-butyllithium, t-butyllithium, t-butyllithium, i-hexyllithium, benzyllithium, phenyllithium, and decyllithium. Examples of the compound containing a nitrogen lithium bond include lithium monomethyl amide, lithium diethyl guanamine, lithium dipropyl guanidinium lithium, n-hexyl decyl amide, lithium diisopropyl guanamine, and hexamethylene hydrazine. Lithium imide, lithium pyrrolidine, lithium piperidine, lithium penta methylene iminoide, lithium porphyrin, and the like. In addition to the above-mentioned monoorganolithium compound, it is also possible to carry out polymerization by using a polyfunctional organolithium compound in combination. Examples of the polyfunctional organolithium compound include a reaction product of I4-dilithium butane, a second butyllithium and diisopropenylbenzene, 1'3,5-tris(tetra), n-butyllithium and 13-tau And a reaction of divinylbenzene, a reaction of n-butyllithium with a polyacetylene compound, and the like. Further, the organic alkali metal compound disclosed in the specification of U.S. Patent No. 5,7,8, No. 92, the specification of the British Patent No. 2,241,239, and the specification of U.S. Patent No. 5,527,753 can also be used. The organic (tetra) compound is preferably n-butyllithium or a second butyllithium from the viewpoint of easiness of industrial availability and ease of control of polymerization. Α These organolithium compounds may be used alone or in combination of two or more. Examples of the other organic alkali metal compound include an organic sodium compound, an organic potassium compound, an organic ruthenium compound, and an organic ruthenium compound. Specifically, sodium naphthalene, stilbene, and the like can be given. Further, pit alkoxides such as a clock, a nano, and a discharge, a caustic acid salt, a carbonate, a brewing amine, and the like can be given. X can also be used in combination with other organometallic compounds. The soil-measuring metal compound 'is an organomagnesium compound, a compound, an organotin compound, or the like. Specific examples thereof include dibutylmagnesium, ethylbutyl or propylbutyl, and the use of a calcined alkoxide, a sodium chloride, a carbonate, a captanamine, etc. . These organic alkaline earth metal compounds may also be used in combination with a metal test compound or other organometallic compound. In the present embodiment, the "co-doprene-based polymer" is preferably obtained by growing an anion polymerization reaction by using the above-mentioned metalloid compound and/or a soil-measuring metal compound as a polymerization initiator. The co-diene polymer is particularly preferably a polymer having an active terminal obtained by a reaction of a ionic polymerization filament, whereby a modified total light dibasic polymer having a high reforming ratio can be obtained. The polymerization method is not particularly limited, and it can be carried out by a batch method or a polymerization method such as a continuous method in which two or more reactors are connected. In particular, it is preferable that the polymerization step is a continuous type and the molecular weight relative to the surface polymer can be stably produced. In the case of listening to the second compound, the sum of the C-axis and the B-block = (7 hindering the change in the later description. Therefore, the sum of the impurities) is preferably 2〇〇. Below ppm, more preferably (10) = and preferably one. Examples of the propylene disaccharide include 1,2-butene and the like. As the acetylenes, for example, fast, vinyl acetylene and the like. The polymerization of ethyl bionide = diterpene polymer is preferably carried out in a solvent. The agent 'for example' may, for example, be a hydrocarbon-based solvent such as a saturated hydrocarbon or an aromatic smoke. Specifically, 5' may be an aliphatic hydrocarbon such as butane, pentane, hexane or heptane. Cyclopentane μ 150826.doc 13 ι 201120073 Cycloaliphatic hydrocarbon such as toluene or dimethyl rape I burn; stupid, recognized to two A hydrocarbon and a smoke or the like comprising the mixture. For , ,’. It is preferred to treat the susceptibility or the fast-acting compound with an organometallic compound before the poly& reaction, and there is a tendency to obtain a high concentration of the active compound, and there is a tendency to achieve a higher rate of reforming. In the polymerization reaction of a common light diene polymer, in order to randomly copolymerize an aromatic vinyl compound and a common diterpene compound, it is used as a chemical agent for controlling the microstructure of the dilute portion of the group. 'Or to improve the polymerization rate, etc., a small amount of polar compounds can also be added. Further, as the polar compound, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dioxime ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxy group can be used. Stupid, 2, 2_ bis (2_tetrahydrocarbamate) propylamine, etc.: class, tetramethylethylenediamine, diphenyl sulfonium dicarboxylic acid 'trimethylamine, triethylamine. A tertiary amine compound such as a pyridine or a chlorinated compound; an alkali metal alkoxide compound such as potassium third potassium pentoxide, potassium hexoxide, sodium butoxide or sodium pentoxide; or a phosphine compound such as triphenylphosphine. These polar compounds may be used alone or in combination of two or more. The amount of the polar compound to be used is not particularly limited, and is selected depending on the purpose and effect. It is usually 0.01 to 100 moles per mole of the polymerization initiator. Such a polar compound (vinylating agent) can be used as a regulator of the microstructure of the conjugated olefin moiety of the polymer and can be used in an appropriate amount depending on the desired amount of vinyl bond. More polar compounds have an effective randomization effect in the copolymerization of a conjugated diene compound and a sulphur-based compound, and can be used as an adjustment of the distribution of an aromatic vinyl compound or a styrene-embedded- 14· 150826.doc Adjusting agent in paragraph 201120073. For the first dry clump ±c _ Λ m regularization ... compound and aromatic vinylation 1 method 'can also be used as the patent special opening " Ding ~ contained in the middle of the copolymerization intermittently add I, 3 - Butadiene - part of the method. The polymerization temperature is not particularly limited as long as it is a temperature at which a polymerization reaction such as living anionic polymerization is carried out. From the viewpoint of productivity, it is preferably (TC or more), and it is sufficient to confirm (4) the modifier of the living end after the end of the polymerization. From the viewpoint of the amount of the reaction, it is preferably 120 or less. Further, in view of preventing the cold flow of the conjugated diene polymer, a polyfunctional aromatic compound such as divinylbenzene for controlling branching may be used. The vinyl group compound is not particularly limited, and is preferably 50 to 1% by mass, more preferably 6 to 8 inches. Further, the amount of the bonded aromatic vinyl group in the conjugated diene polymer of the present embodiment is not particularly limited, but is preferably 5% to 5% by mass, more preferably 2 〇 to 4% by mass. When the amount of the bonded conjugated diene and the amount of the bonded aromatic vinyl group are in the above range, a vulcanized rubber which is excellent in balance between low hysteresis loss and wet skid resistance and which also satisfies wear resistance or fracture strength can be obtained. ^Here, the bonded aromatic vinyl fluorene can be UV-activated by phenyl The amount of the bonded conjugated diene can also be determined by measurement with light. Specifically, it can be measured by a method based on the examples described later. Further, the amount of vinyl bond in the conjugated diene bonding unit It is not particularly limited, and is preferably from 10 to 75 mol%, more preferably from 25 to 65 mol%/❶. If the amount of the ethylene bond is in the above range, low hysteresis loss and wet skid resistance can be obtained. 150826.doc -15- 201120073 Vulcanized rubber with better balance and also satisfying wear resistance or breaking strength. Here, in the case where the modified conjugated diene polymer is a copolymer of butadiene and styrene The amount of vinyl bond in the butadiene bonding unit can be determined by the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)) (1, 2 bonding amount) The microstructure (the amount of each bond in the modified conjugated diene polymer) is within the above range, and further, when the glass transition temperature of the copolymer is in the range of -45 to -15 ° C, low Vulcanized rubber with better balance between hysteresis loss and wet skid resistance. Regarding glass transition temperature, according to IS0227 68: 2006, the DSC curve is recorded while the temperature is raised within a specific temperature range, and the peak of the DSC differential curve (Inflection point) is set as the glass transition temperature. The conjugated diene polymer of the present embodiment is a total of vehicles. In the case of a diene-aromatic vinyl copolymer, it is preferred that the number of blocks in which 30 or more aromatic vinyl units are connected is small or absent. Specifically, the copolymer is dibutyl In the case of a styrene copolymer, the polymer is decomposed by the method described by Kolthoff (IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946), and analyzed to be insoluble in sterol In the known method of the polystyrene amount, the block in which 30 or more aromatic vinyl units are bonded is preferably 5% by mass or less, and more preferably 3% by mass or less based on the amount of the polymer. In the method described above, after obtaining a conjugated diene polymer having an active terminal, the modified conjugated diene polymer of the present embodiment can be obtained by the following modification step, and the upgrading step is carried out. The modifier is reacted with the active terminal of the above-mentioned conjugate 150826.doc •16-201120073 monoolefin polymer. The modifier has one or more nitrogen atoms and a heterocyclic ring containing two or more, and has Two or more compounds having a decyl group having two or more alkoxy groups bonded thereto. By using a compound having more than j or more heterocyclic rings containing two or more nitrogen atoms and a hydrocarbon, and having two or more anthracene groups having two or more alkoxy groups bonded thereto as a modifier A bond is formed between the terminal of the olefinic polymer and the si. The above compound used as a modifier is preferably a decyl group in which all of the decyl group is bonded with 3 alkoxy groups. By using the compound as a modifier, the reactivity of the modified oxime or the interaction with other compounds can be further improved, and the processability of the modified conjugated diene polymer obtained can be further improved. . Among the above, a modifier as a compound represented by the following formula (1) is preferred. The bond between the terminal of the conjugated diene polymer and the Si can be more effectively formed by efficiently reacting the alkoxylated group of the following formula (1) with the active terminal of the common dibasic polymer. [7] p7 (Rl〇)~f'R~K 8^-r^s,-(〇r2)(1) RL n K(3_n), R丨~R4 are independent, respectively, indicating carbon number 丨~2〇 Alkyl or aryl, R and R: independently, representing a carbon number of 2 伸 alkyl, r, r8 are independently 'representing a hydrocarbon group of carbon 1-6, 'S adjacent to the two N-forming 5 members The ring structure above the ring, the claws and the 11 are independent, respectively, and represent an integer of 2 or 3.) The modifier as shown in the above formula (1) is, for example, 1'4-double [3_(three 150826.doc -17- 201120073 methoxy decyl) propyl] piperazine, 1,4-bis[3-(triethoxydecyl)propyl] piperene, 1,4 bis[3-(dimethoxymethyl)矽alkyl)propyl]pitricin, hydrazine, 3_bis[3_(dimethoxyfluorenyl)propyl]imidazolidinium, 1,3-bis[3-(triethoxydecyl)propyl]imidazole Pyridine, 13-bis[3-(dimethoxyethylindenyl)propyl]m0, bite, 1,3_bis[3-(trimethoxysulphonyl)propyl]hexahydropine bite, Further [3. (diethoxy oxalate) propyl] hexammine mouth bit, ι, 3 · bis [3_(tributyloxylinyl) propyl]-1,2,3,4-tetra Hydropyrimidine and the like. Among these, the viewpoint of the reactivity of the modifier, the interaction with other compounds such as an inorganic filler such as ruthenium dioxide, or the processability of the modified conjugated diene polymer obtained For example, 'm is preferably m and η are ^. Specifically, it is preferably 1,4-bis[3-(trimethoxydecyl)propyl]piped, bismuth [3_(diethoxydecyl)propyl]pitricin, 13_double [ 3-((trimethoxydecyl)propyl]imidazolium, 1,3 bis[3-(triethoxydecyl)propyl]imidazolidinium, 込3 again [3-(dimethoxy oxalate) )propyl] hexahydropyrimidine, bis[3_(triethoxydecyl)propyl]hexahydropyrimidine, 13 bis[3(tributyloxydecyl)propyl]-1,2,3,4- Tetrahydropyrimidine, among these, more preferably 14 pairs of [3_(dioxaxolysin)propyl]piperazine, ^ an bis-(triethoxydecyl)propyl] pi well . In the above-mentioned agent, as long as it does not cause a significant adverse effect on the reforming reaction or the like, other compounds such as an intermediate such as the above-mentioned modifier or the like of the modifier may be contained. Further, if it is within the range in which the effects of the embodiment are obtained, other conventionally known modifiers may be used in combination. The reaction temperature, reaction time, and the like when the modifier is reacted with the polymerization active terminal are not particularly limited, and it is preferably in the reaction or higher. 150826.doc 201120073 With respect to the above modifier, the total number of moles of the alkoxy group bonded to the decyl group in the compound is preferably in the range of 0.8 to 3 times the number of added moles of the polymerization initiator. More preferably, it is in the range of 1 to 2.5 times, and further preferably in the range of 1 to 2 times. From the viewpoint of obtaining a sufficient reforming ratio of the modified conjugated diene-based polymer obtained, it is preferably 0.8 times or more, and from the viewpoint of the cost of the modifier, it is preferably 3 times. the following. Further, from the viewpoint of improvement in workability, it is preferred to couple the polymer terminals to each other to obtain a branched polymer component. In view of the fact that the effect of the present embodiment is more excellent, it is preferred to produce a modified conjugated diene polymer which is preferably contained in an amount of preferably 5% by mass or more, more preferably 20% by mass or more, and further A polymer of a polymer containing a functional group component (a modified conjugated diene polymer modified by a modifier) is preferably 50% by mass or more. The method for quantifying a polymer containing a functional group component can be measured by a chromatography method capable of separating a modified component containing a functional group from a non-modified component. As a method of using the chromatographic method, a GPC column using a polar substance such as ceria which adsorbs a functional group component as a filler is used, and the internal standard of the non-adsorbed component is used for comparison and quantification. The number average molecular weight (?η) of the polystyrene-equivalent converted by the gel permeation chromatography (GPC) of the modified conjugated diene polymer of the present embodiment is preferably 20,000 to 2,000,000, more preferably 100,000~ 1,000,000, further preferably 200,000 to 600,000, and more preferably 300,000 to 400,000. By setting the molecular weight of the lower limit or more, the strength at the time of producing the vulcanized rubber can be further increased, and by setting the molecular weight of the above upper limit or less, the workability can be further improved by 150826.doc -19-201120073. Further, from the viewpoint of the physical properties of the vulcanized rubber, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (?η) is preferably 丨.05 to 3. 〇, more preferably 2布 2 5 . In the method for producing the modified conjugated diene polymer of the present embodiment, after the modification reaction, a deactivator or a neutralizing agent may be added to the m towel as needed. Examples of the deactivating agent include water; alcohols such as methanol, ethanol, and isopropanol. The neutralizing agent may, for example, be a carboxylic acid such as hard acetic acid, oleic acid or tereic carbonic acid; an aqueous solution of a mineral acid; or a carbonic acid gas. Further, it is preferable to add rubber to the modified conjugated diene polymer of the present embodiment from the viewpoint of preventing the formation of the condensate after the polymerization, or the stability during processing. Use a stabilizer. The stabilizer for rubber is not particularly limited, and a known one may be used, and preferably 2,6-di-t-butyl-4-hydroxyf-benzene (BHT) or n-octadecyl- 3 (4, hydroxy_3, 5) , di-tert-butylphenol) propionic acid, 2-methyl-4,6-bis[(octylthio)methyl]phenol, and the like. Further, in order to improve the processability of the modified conjugated diene polymer of the present embodiment, it is necessary to add a filler oil to the modified conjugated diene polymer. The method of adding the extender oil to the modified conjugated diene polymer is not particularly limited, and it is preferred to carry out solvent removal by adding the filler oil to the polymer solution and mixing to prepare an oil-extended copolymer solution. method. Examples of the extender oil include aromatic oils, naphthenic oils, and paraffin oils. Among these, in terms of environmental safety, or prevention of oil spill and wet grip characteristics, it is preferable that the polycyclic aromatic (PCA) component of the IP346 method is 3% by mass or less of aromatic oil. Product. As an aromatic oil substitute, it can be mentioned

Kautschuk Gummi Kunststoffe 52 (12) 799 (1999) Eight of the eight 150826.doc •20· 201120073 Ship E^M/S, etc., and (4). The amount of the filler oil to be added is not particularly limited. The amount of the compound is from (4) to 1 part by mass of the modified copolydiene polymer. The Berry injury is preferably 20 to 37.5 parts by mass. A well-known method can be used as the method of obtaining the modified di-diuretic polymer of the present embodiment from the polymer solution. For example, a method of separating a solvent by steam A, separating and filtering ', ^ ^ w, and then dehydrating and drying the polymer, and taking the polymer; using the rinsing tank to carry out the squeezing, and then using the squeezing method The method of taking off the machine, etc. A modified total light dibasic polymer which is suitable for use as a vulcanized rubber factory can be obtained by using a barrel-type dry inorganic or the like in a straight state. For example, the polymer can be obtained by the following method: ;, inorganic filler or slave: etc.,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Mixing agent, vulcanization accelerator, auxiliary agent, etc., to make a modified total light dilute group::: After the object, heat and vulcanize. Among these, it is preferred to prepare a rubber component comprising the modified co-administration-ruthenium-assisted octa-ene-based polymer of the present embodiment and a modification of the inorganic filler of the cerium oxide cerium oxide. Women's polymer composition. When the oxidized W inorganic filler is dispersed in the modified conjugated polymer of the present embodiment to form a vulcanized rubber, the balance between low hysteresis loss and wet skid resistance is excellent, and it is practically sufficient. High abrasion resistance or damage: Eight can give excellent processability. When the modified conjugated diene composition of the present embodiment is used in a vulcanized rubber application such as an automobile or a shoe such as a tire or a vibration-proof rubber, it is also preferable to contain a silica dioxide inorganic inorganic 150826.doc - 21· 201120073 Filler as a reinforcing filler. In the copolymer-based polymer composition, the rubber-like polymer other than the modified light-dense polymer of the present embodiment can be used in combination with the modified polymer of the present embodiment. Examples of such a rubbery polymer include a copolymerized diene polymer or a hydrogenated product thereof, a random copolymer of a conjugated diene compound and an ethyl fluorene aromatic compound, or a hydride thereof, or a conjugate thereof. A block copolymer of a monoolefin compound and a vinyl aromatic compound or a hydrogenated product thereof, a non-diene polymer, a natural rubber or the like. Specific examples thereof include butadiene rubber or a hydrogenated product thereof, isoprene rubber or a hydrogenated product thereof, styrene-butadiene rubber or a hydrogenated product thereof, styrene-butadiene block copolymer or A styrene-based elastomer such as a hydride styrene-isoprene block copolymer or a hydride thereof, an acrylonitrile-butadiene rubber or a hydrogenated product thereof. Examples of the non-diene polymer include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, and ethylene-octene rubber. Olefin-based elastomer, butyl rubber, bromobutyl rubber, acrylic rubber, fluororubber, ruthenium rubber, vaporized polyethylene rubber, epichlorohydrin rubber, α, β. unsaturated guess - acrylic acid vinegar - Conjugated diene copolymerized rubber, amine ester rubber, polysulfide rubber, and the like. Each of the above rubbery polymers may be a modified rubber to which a functional group having a polarity such as a hydroxyl group or an amine group is imparted. Further, from the viewpoint of balance between performance and processing characteristics, the weight average molecular weight thereof is preferably 2, (10) G 2 , qing, _, more preferably 5,000 to 1,500, 00 (^, and low molecular weight may also be used. The rubbery polymer may be used alone or in combination of two or more. J 50S26.doc •22· 201120073 The conjugated conjugated decadiene polymerization product of the present embodiment is prepared. In the case of the modified conjugated diene polymer composition of the above rubbery polymer, the ratio of the ratio (mass ratio) to the balance of the dibasic polymer/rubber polymer is preferably 20 /80~100/0, more preferably 3〇/7〇~9〇/1〇, and further preferably 5G/50~8〇/2〇1 modified total two-dimer polymer/rubber polymer When the blending ratio is in the above range, a vulcanized rubber which is excellent in balance between low hysteresis loss and wet skid resistance and which is more resistant to abrasion resistance or breakage strength can be obtained. The niobium oxide-based inorganic filler is not particularly limited. A known one may be used, preferably a solid particle containing Si〇2 or SisAl as a structural unit, more preferably Si〇4Si3Ai is a main component of the structural unit. Specific examples of the dioxide-based inorganic fillers include dioxane, clay, talc, mica diatomaceous earth, ash stone, montmorillonite, zeolite, and glass. As the inorganic fibrous material such as fibers, a mixture of a silica-based inorganic filler which hydrophobizes the surface, or a mixture of a cerium oxide-based inorganic filler and an inorganic filler other than cerium oxide can be used. From the viewpoint of reinforcing property, cerium oxide and glass fiber are preferred, and cerium oxide is more preferred. As the dioxide dioxide, dry-type % dioxide, wet type dioxide, and synthetic cerium salt can be cited.矽 矽 矽 。 。 。 。 。 。 。 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 湿 湿 湿 湿 湿 湿 湿 湿 湿 湿 湿 湿 湿 湿 湿 湿 湿 湿From the viewpoint of obtaining practically good abrasion resistance or destructive properties, the gas adsorption specific surface area obtained by the inorganic filler by the adsorption-resistant method is preferably 1 〇〇 to over m 2 /g, more Good, 25Gm2/g. Also as needed The specific surface area can be relatively small (for example, 2〇〇), which has a relatively small surface area (for example, a rare earth oxide inorganic filler with a specific surface area of less than 2〇〇m2/g) and a specific surface area (for example, 2〇〇). The claws and one of the above cerium oxide-based inorganic fillers are used in combination. Thereby, good abrasion resistance or failure characteristics and high hysteresis loss can be highly balanced. The amount of the sulfur dioxide-based inorganic filler in the composition is preferably 0.5 in terms of 1 part by mass of the rubber component containing 2 parts by mass or more of the modified co-light diene polymer of the present embodiment. ~ 300 parts by mass, more preferably 5 to 2 parts by mass, and further preferably = ~! 〇〇 mass parts. In view of the effect of the addition of the inorganic filler, the amount of the oxidized 11-based inorganic filler is preferably 〇$ parts by mass or more, and the inorganic filler is sufficiently dispersed to impart processability to the composition. In view of the fact that the mechanical strength is practically sufficient, it is preferably 300 parts by mass or less. The modified conjugated-olefin polymer composition may also contain carbon black. The carbon black is not particularly limited, and for example, two types of carbon blacks such as SRF, FEF, guess, isaf, and _ can be used. Among these, it is preferable that the nitrogen adsorption specific surface area is 50 m'g or more, and the dibutyl phthalate_p) oil absorption amount is carbon black having a rib ratio of (10) g or more. The amount of the carbon black to be added is preferably 0.5 parts by mass or more, more preferably 5 parts by mass, more preferably 5 parts by mass, based on 100 parts by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment. Share. The blending amount is preferably 〇5 parts by mass or more from the viewpoint of performance required for use in applications such as tires, such as tires and conductive tires, and is preferably from the viewpoint of dispersibility. It is set to 100 mass parts or less. 150826.doc •24- 201120073 Further, the modified conjugated diene polymer composition may contain a metal oxide or a metal hydroxide in addition to the cerium oxide inorganic filler or carbon black. The term "metal oxide*" means a solid particle which is a main component of a structural unit, and a metal atom represented by the chemical formula MxCMM, and X and y respectively represent an integer of the formula 6, and for example, alumina, titania, magnesia, zinc oxide or the like can be used. Further, a mixture of a metal oxide and an inorganic filler other than the metal oxide is also used. The metal hydroxide is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, and hydrazine hydroxide. The co-diene polymer composition may also contain a money coupling agent. The shoal coupling agent has a function of making the rubber component and the silica sand-based inorganic filler to interact closely, and contains a base for the affinity or bonding property of the rubber component and the cerium oxide-based inorganic filler. + system 4 = one molecule has a sulfur-bonded moiety with an alkoxy group, and (iv) an alcohol group: =. Things. Specifically, s ' can be exemplified by a double case of triethoxy shi _: kib tetrasulfide ", bis [3 · (triethoxy ketone) propyl disulfide, bis-[2- (two Ethyl-based yarn-based base)_ethyl]_tetrasulfide. The blending amount (4) is preferably from 0. 1 to 30 parts by mass, more preferably from 0.5 to 20 parts by mass, based on the above-mentioned dioxic inorganic filler, preferably from 5 parts by mass. If the money coupling agent is adjusted, the above-mentioned addition effect of the hydrazine coupling agent can be made more remarkable. The modified 'modified coplanar diterpene polymer composition may also contain a softener for rubber. As a rubber oil, or a liquid or low molecular weight synthetic softener. ^乂佳 is made by the improvement of mineralization, compatibilization and processability: the softness of rubber is called processing oil or filling 150826.doc -25- 201120073 The mineral softener for rubber is the aromatic ring and ring. Mixture of alkane ring and rocky soil chain 'The carbon number of the paraffin chain accounts for 50〇/〇 in the total carbon number. It is called the stone snail system. The ring number of the ring is 30~45%. An aromatic carbon number of more than 30% is called an aromatic system. The rubber softener used in combination with the modified conjugated di-alkaline-vinyl copolymer of the present embodiment preferably has a tendency to have a copolymer having a moderate aromatic content, and is preferred. The amount of the rubber softener to be added is preferably 〇1 to 1 part by mass, more preferably 10 to 90 parts by mass, per part by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment. Further, it is preferably 3 Å to 9 Å by mass. By setting the amount of the softener for rubber to 1 part by mass based on the rubber component, it is possible to suppress the bleeding or the viscosity of the surface of the composition. Method for mixing modified conjugated diene polymer of the present embodiment, other rubbery polymer, cerium oxide inorganic filler, carbon black or other filler, decane coupling agent, rubber softener # additive There is no particular limitation. For example, a melt-kneading method using a general mixer such as an open roll, a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, or a multi-screw extruder; After that, the method of removing the agent is heated. Among these, from the viewpoint of productivity and good mixing, it is preferable to use a melting method of a drum, a Banbury mixer, a kneader, and an extruder. Further, any one of the modified total light diuretic polymer and the various compounding agents-sub-H practice can be used and mixed into a plurality of times. The modified conjugated diene polymer composition can also be made into a vulcanization composition which is vulcanized by a vulcanizing agent. As the vulcanizing agent, for example, a radical generating agent such as an organic peroxide or an azo compound, an anthraquinone compound, an anisine compound, a polyamine compound, a sulfur or a sulfur compound can be used. The sulfur compound contains sulfur monochloride, sulfur dichloride, a disulfide compound, a polymer polysulfide, and the like. The amount of the vulcanizing agent to be used is usually 0.1 to 15 parts by mass per 1 part by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment. As the vulcanization method, a previously known method can be used, and the vulcanization temperature is usually from 12 Torr to 2 Torr ° C, preferably from 140 to 180 Torr C. Further, when vulcanization is carried out, a vulcanization accelerator may be used as needed. As the vulcanization accelerator, a conventionally known material can be used, and examples thereof include a sulfoximine system, a pulse system, a thiura system, a disc-amine system, a cis-ammonia system, a system, a sulfur gland system, and a dithiol group. A vulcanization accelerator such as a formate ester or the like can be used as a vulcanization aid to make a white material or a hard acid. The amount of the vulcanization accelerator to be used is usually G.G1 to 2G parts by mass, preferably (M to 15 parts by mass) per 100 parts by mass of the rubber component containing the modified conjugated diene polymer of the present embodiment. In the modified total diene polymer composition, other softeners or fillers other than the above may be used, and heat-resistant stabilizers and antistatic agents may be used as long as the object of the embodiment is not impaired. Various additives such as weathering stabilizers, anti-aging agents, coloring agents, lubricants, etc. As other secrets, known softeners can be used. As other fillers, specific examples thereof include carbonic acid, carbonic acid, and magnesium. Aluminum sulfate, barium sulfate, etc. As the above-mentioned heat stabilizer, antistatic agent, weathering stabilizer, anti-aging agent, colorant, and lubricant, known materials can be used. 150826.doc •27- 201120073 [Examples] The present embodiment will be described in more detail by way of the following examples. However, the present embodiment is not limited to the following examples. Further, the analysis of the sample is carried out by the method described below. Amount of styrene 4 samples were made into a chloroform solution, and the amount of bonded styrene was measured by absorption of phenyl uv 254 of stupid ethylene (manufactured by Shimadzu Corporation: UV-2450) 〇(2) microstructure of butadiene portion ( 1,2·vinyl bond amount) The sample is made into a carbon disulfide solution, and the infrared spectrum is measured in a range of 6 〇〇 to 1 〇〇〇 cm·1 using a solution tank, and the absorbance at a specific wave number is According to the calculation method of Hampton's method, the microstructure of butadiene was obtained (manufactured by Sakamoto Seiki Co., Ltd.: FT-IR230). (3) Mona viscosity is based on JIS K 6300, at 100X: preheating for i minutes, The viscosity after 4 minutes was measured. (4) Molecular weight and molecular weight distribution The chromatogram was measured using a gel permeation chromatograph (GPC) using three columns of a polyethylene penta gel as a filler. The weight average molecular weight (Mw) and the number average molecular weight (?n) were determined from a weighting curve using a standard polyethylene, and the molecular weight distribution index (Mw/Mn) was calculated from the ratio of the weight average molecular weight to the number average molecular weight. Use tetrahydrofuran (THF). Use: Protection column: Tosoh TSKguardcolumnHHR- 150826.doc •28- 201120073 Η, column: Tosoh TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR. Use Tosoh at an oven temperature of 40 ° C and a THF flow rate of 1.0 mL / min. The manufactured HLC8020 RI detector was used to measure the molecular weight. 10 mg of the sample was dissolved in 20 mL of THF, and 200 pL of the solution was injected into the apparatus for measurement. (5) Glass transition temperature (Tg) According to IS022768: 2006, using DSC3200S manufactured by MAC Science, under the circulation of helium gas of 50 mL/min, the temperature was raised from _100 °C at 20 °C/min. In the DSC curve, the Inflection point of the DSC differential curve is taken as the glass transition temperature. [Example 1] Two autoclaves having an internal volume of 10 L, an internal height to diameter ratio (L/D) of 4, an inlet at the bottom, an outlet at the top, and a mixer having a stirrer and a temperature adjustment sleeve were connected in series. The first block was used as a polymerization reactor and the second block was used as a reforming reactor. Mixing with butadiene 16.0 g/min, styrene 8.0 g/min, and n-hexane 125.6 g/min to remove impurities such as moisture, and further inerting the impurities, and adding them to the first block The reactor was previously mixed with 0.075 mmol/min of n-butyllithium (treated with n-butyllithium) using a static mixer and continuously fed to the bottom of the first reactor, which was then used at a rate of 0.020 g/min. The polar substance 2,2-bis(2-tetrahydrofuryl)propane was supplied to the bottom of the first reactor, and n-butyllithium as a polymerization initiator was supplied to the first reactor 150826 at a rate of 0.150 mmol/min. .doc -29- 201120073 At the bottom, the internal temperature of the reactor outlet was 90 ° C, and the polymerization was continued. The temperature of the second reactor was maintained at 85. (:, 1,4-bis[3-(trimethoxydecyl)propyl] piperazine as a modifier was added from the bottom of the second reactor at a rate of 0.0375 mmol/min, and the modification was carried out (coupling) The reaction was continuously added to the polymer solution flowing from the top of the second reactor in a manner of 0.048 g/min (n-hexane solution) in a manner of 0.2 g per 100 g of the polymer (BHT). After the completion of the reforming reaction, the solvent is removed to obtain a modified conjugated diene polymer. Further, the modified conjugated second is added to 37 parts by mass per 1 part by mass of the polymer. After adding S-RAE oil (NC-140 manufactured by JX曰石曰石能源股份有限公司) to the olefin polymer solution, the solvent was removed by a barrel dryer to obtain an oil-filled modified conjugated diene polymer (test Sample A). The Mona viscosity of sample A at 10 °C is 80.0, and the weight average molecular weight of the polystyrene exchange measured by GPC is 908,000, and the number average molecular weight is 393,000. As a result of the measurement of the sample, the amount of bonded styrene was 33% by mass, and B in the butadiene bonding unit The amount of base bond (1,2-bond amount) was 38 mol%, and the glass transition temperature measured by DSC was _25 ° C. [Example 2] In addition to 1,4-double as a modifier An oil-extended modified conjugated diene polymer (sample B) was obtained in the same manner as in Example i except that the addition amount of 3-(tridecyloxydecyl)propyl]piper was set to 0.0563 mmol/min. The analysis results of the sample B are shown in Table 1. [Example 3] Except that the modifier was replaced by M-bis[3-(tridecyloxydecyl)propyl] piperene 150826.doc • 30 · 201120073 An oil-filled modified conjugated diene polymer was obtained in the same manner as in Example 1, except that 1,4 - bis[3 - (diethylene gas-based breaker) propyl] was used. Example c) The analysis results of the sample C are shown in Table 1. [Example 4] except that the modifier was replaced by 1,4-bis[3-(trimethoxydecyl)propyl]periole 1,4-Bis[3-(dimethoxymethylmethyl sulfanyl) propyl]α bottoming, and the addition amount was set to 0.0563 mmol/min, and oil-filled modification was obtained in the same manner as in Example i. The conjugated diene polymer (sample D). The analysis results of the sample D are shown in Table 2. Example 5] except that the modifier was replaced by 1,4-bis[3-(tridecyloxydecyl)propyl] piperazine to 1,3-bis[3-(trifoxydecyl)propane An oil-extended modified conjugated diene polymer (sample E) was obtained in the same manner as in the actual target example 1 except for the hexahydropyrimidine. The analysis results of the sample E are shown in Table 2. [Comparative Example 1] In addition to changing the modifier from i,4-bis[3-(trimethoxysulphonyl)propyl] brigade to bis[3-(dimethoxyoxyalkyl)propyldimethylamine An oil-extended modified total diuretic polymer was obtained in the same manner as in Example 1 (samples... The analysis results of the sample F are shown in Table 3. [Comparative Example 2], except that the modifier was replaced by M-bis[3_(trimethoxysulphonyl)propyl group, and the same was carried out except for the di-poly (3·diethoxy group, alkyl group). (1) An oil-extended modified conjugated diene polymer (sample G) e was obtained in the same formula. The analysis results of the sample G are shown in Table 3. 150826.doc

-31-S } 201120073 [Comparative Example 3] The addition amount of n-butyl lithium to be polymerized was set to 〇12〇mm〇1/min, and the amount of 2,2-bis(2-tetrahydrofuryl)propane was set. For 〇〇18 g/min, the modifier was replaced by 1,4-bis[3_(trioxanyloxy)propyl] to 丨_ · (diethoxy fluorenyl) propyl An oil-extended modified conjugated diene polymer (sample H) was obtained in the same manner as in Example 除 except that the amount of the mixture was changed to 〇13 〇mmol/min. The analysis results of the sample were shown in Table 3. [Table 1] Example 1 Example 2 Example 3 Reagents ΝΓγϊ AB c Polymerization conditions J-ene (g/min) 16.0 16.0 160 Ethylene (g/min) 8.0 8.0 8,0 正&院- ( g/min) 125.6 125.6 _ 125.6 (mmol/min)~ 90 0.075 90 — — 0.075~~ 90 ~~6.075~~ Initial polymerization of butyl butyl (mmol/min) 0.150 0.150 〇150 Addition to the sex page (g /min) 0.020 0.020 〇020 Modifier modifier type*2 BTMSP BTMSP BTESP Addition amount (mmol/min) 0.0375 0.0563 0.0375 Lithium equivalent ratio 1.0 1.5 1.0 Minute if value bonding phenethyl hydrazine ^ 昙τττ'Ξ- -- Weight (mass. / 〇) 33 33 33. Teacher weight (mol%) 38 38 38 Glass transfer temperature (. 〇-25 -25 ~~ -25 Weight average molecular weight (Mw) (million) 90.8 87.0 82 4 number average molecular weight (Μη) (million) 39.3 ^39.9 37.9 Mw/Mn 2.31 2 1S ~~2Λ7 77 % $•5 phr after oil filling with Mona viscosity (ι〇〇°〇80.0 89.7 wood 1 2, double (2-tetrahydrofuranyl)propane-- 氺2 BTMSP : 1,4·bis[3-(trimethoxydecyl)propyl] piperene BTESP: 1,4-double [3-(triple-three) The total amount of alkoxy groups bonded to the decyl group contained in the modifying agent added to the oxyalkylalkyl)propyl]piperazine*3 is relative to the total addition amount of the molar ratio ' / / * butyl chain 150826. Doc •32· 201120073 [Table 2] Example 4 Example 5 Paper Hemp • ΓΝΟ. ------ DEJ — Pei (g/min) 16.0 16.0 Benyi' -- (g/min) 8.0 8.0 Hospital (g/min) 125.6 125.6 Polymerization CT temperature _degree (°C) 90 90 Strip 4k butyl butyl clock (mmol/min) 0.075 0.075 1 〇 Start stop Ding Mou (mmol / min) 0.150 0.150 Polar substance 1 added I (g/min) 0.020 0.020 Modifier _ Modifier type ^ BDMMSP BTMSHP Addition amount (mmol/min) 0.0563 0.0375 Lithium equivalent tP3 1.0 1.0 Bonded styrene amount (% by mass) 33 33 Ethylene Base bond amount (mol%) 38 38 parts Glass transition temperature (°C) -25 -25 Analytical weight average molecular weight (Mw) (million) 74.6 88.8 Value number average molecular weight (Μη) (million) 35.2 38.2 Mw/Mn 2.12 2.32 37_5 phr after oil filling with Mona viscosity (i〇〇°C) 57.9 78.9 *1 2,2_bis(2-tetrahydrofuryl)propane 氺2 BDMMSP : l, 4-bis[3-(dimethoxymethylxanthyl)propyl]piperazine BTMSHP : 1,3-bis[3-(trimethoxydecyl)propyl]hexahydropyrimidine*3 = added The molar ratio of the total amount of alkoxy groups bonded to the ruthenium alkyl group in the modifier is λ. 150826.doc 33- 201120073 [Table 3] BTMSA: double (3-tridecyloxydecylpropyl)_N_methylamine BTESE: 1,2-bis(3-triethoxyindolyl)ethane TESMP ·' 1_[3-(triethoxy shixi The total amount of alkoxy groups bonded to the alkylene group contained in the modifier added to the alkyl)propyl]_4_methylpiperidin 13 is added to the total amount of the n-butyl group in addition to n-butyl<Comparative Example 1 Example 2 Comparative Example 3 Sample No. FG 聚合 Polymerization conditions butyl hydrazine (g/min) 16.0 16.0 16.0 phenylethyl baking minutes) 8.0 8.0 8.0 n-hexane (four) minutes) 125.6 125.6 125.6 polymerization temperature fc) 90 90 90 Base (mmol/min) 0.075 0.075 0.075 Polymerization starting n-butyllithium iVrnnnl/mm, 0.150 0.150 0.120 Polar substance 1 addition amount (β/min) 0.020 0.020 0.018 Modifier modifier BTMSA BTESE TESMP Addition amount (mmol/min) 0.0375 0.0375 0.13 (8) Lithium equivalent 1.0 1.0 2.0 Minute ik Value Bonding phenethyl group ^ Quantity (% by mass) 33 33 33 Ethylene bond amount (mol%) 38 38 39 Glass transition temperature (. 〇-25 -25 -25 Weight average molecular weight (Mw) (million) 90.1 90.1 71.7 Amount of average molecular weight (Μη) (million) 38.4 39.7 37.2 Mw/Mn 2.35 2.27 1.93 A 37_5 phr oil-filled Mona viscosity (100 ° C 75.1 74.8 54.9 = bis(2-tetrahydrocyanpropane [Examples 6 to 1 〇, Comparative Examples 4 to 6] The samples (samples A to H) shown in the above Tables 1 to 3 were used as raw materials. Rubber and knee, a rubber composition containing each raw material rubber was obtained according to the following formulation. Oil-filled modified conjugated diene polymer (samples A to H): 137.5 parts by mass of oxidized hair (manufactured by Evonik Degussa Co., Ltd.) , Ultrasil VN3): 75.0 parts by mass of carbon black (manufactured by Tokai Carbon Co., Ltd., Seat KH (N3 39)): 5.0 parts by mass 150826.doc • 34· 201120073 Shi Xiyuan coupling agent (manufactured by Evonik Degussa, Si75): 6.0 quality S-RAE oil (manufactured by JX曰 Mine Waste Energy Co., Ltd., J〇MO Process 1^(:140): 4.5 parts by mass of zinc white: 2.5 parts by mass of stearic acid: 1.5 parts by mass of anti-aging agent (N-isopropyl Base-Ν'-phenyl-p-p-diamine): 2.0 parts by mass of sulfur: 2.2 parts by mass of vulcanization accelerator (Ν-cyclohexyl-2·benzothiazolylsulfinamide) : 1.7 parts by mass of vulcanization accelerator (diphenyl hydrazine): 2.0 parts by mass in total: 240.9 parts by mass of the rubber composition was kneaded by the following method. Using a closed kneading machine equipped with a temperature control device (content amount 〇. 3 L As the first stage of the kneading, the raw material rubber (samples A to H), the filler (cerium oxide, carbon black), and the organic decane coupling agent were prepared at a filling rate of 65% and a rotor rotation speed of 5 〇/57 rpm. The processing oil, the whitening, and the stearic acid are kneaded. At this time, the temperature of the closed mixer is controlled, and the discharge temperature (preparation) is 155 to 160 ° C to obtain a rubber composition. After mixing, the above-obtained formulation is cooled to 5, and the 'W anti-aging agent' is used to enhance the dispersion of the dioxo. In this case, the discharge temperature is also controlled by the temperature control of the mixer. ) Adjust to 155~160. (:. ★ After VP, as the third stage of the kneading, use the setting of 70. (: The opening roller is added with sulfur and vulcanization accelerator for kneading. After that, it is formed in 丄6 generation λ 150826 .doc -35- 201120073 Using sulfur The pressurization was carried out for 20 minutes, and the physical properties of the rubber composition were measured. The physical properties of the rubber composition were measured by the following methods. (1) Modifier viscosity by using a Monner viscometer, i minutes was preheated at 13 °c according to jIS K630H, and then the rotor was rotated at a speed of 2 revolutions per minute, and the viscosity after 4 minutes was measured. The smaller the value, the more excellent the workability. (2) Tensile strength The measurement was carried out by a tensile test method of JIS K6251, and the comparative example* was set to 100 and indexed. (3) Viscoelastic parameters The viscoelastic moxibustion was measured by torsion mode using Rheometric Scientific = ι, "Im rmtlc 黏 黏 黏 黏 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. Each measurement value was indexed by setting Comparative Example 4 to 100. The t-measured under the condition of frequency, frequency ι Hz 'distortion i% is used as an indicator of wetland grip performance. The larger the value, the better the grip performance of the wetland. In addition, a (10) measured at 5 (TC, frequency 1 〇 Hz, distortion 3%) is used as an indicator of fuel economy characteristics. The smaller the value, the better the fuel economy performance. (4) Wear resistance Use the Akron abrasion test machine (Antian pick _ also 丨

According to JIS K6264-2, the load is 44.1 N, and the rotation is made by Manoda Seiki Co., Ltd.

The amount of abrasion of the moxibustion was changed to 1000 times, and the comparative example 4 was set to 100 and indexed. The larger the finger width L is, the more excellent the abrasion resistance is. 0 150826.doc -36- 201120073 [Table 4] Example 6 Example 7 Example 8 Example 9 Example 10 Oil-filled styrene-butadiene copolymerization ABCDE Formulation Mona viscosity 54 63 58 55 57 Vulcanized rubber tensile strength index 111 111 105 104 110 Abrasion resistance index 104 115 113 114 113 0°ctai^ (strain 1%) Index 104 106 104 101 106 50° (: ίαηδ (strain 3%) index 92 87 93 98 91 [Table 5] Comparative Example 4 Comparative Example 5 Comparative Example 6 Oil-filled styrene-butadiene copolymer FG Η Formulation Mengna viscosity 51 58 63 Vulcanized rubber physical property Tensile strength index 100 111 110 Wear resistance index 100 95 101 0°C tans (strain 1%) Index 100 98 108 50°Ctai^ (strain 3%) index 100 116 96 As shown in Tables 4 and 5, confirm implementation The modified conjugated diene polymer compositions of Examples 6 to 10 have lower tan5 at a higher temperature and less hysteresis loss than the compositions of Comparative Examples 4 and 5, achieving low rotational resistance of the tire, and low temperature. Tan3 is high and has excellent wet skid resistance. Further, it is confirmed that the wear resistance and tensile strength are also Further, in the case of comparison with Comparative Example 6, it was confirmed that the viscosity of the blended material was low, and the balance between the workability and the physical properties of the vulcanized rubber was excellent. [Example 11] The inner volume was 10 L, and the mixer and the sleeve were provided. The high-pressure dad, which can control the temperature, is used as a reactor to remove impurities such as 777 g of butadiene, 273 g of styrene, 4800 g of cyclohexane, and 2,2-bis(2-tetrahydrofuryl)propane as a polar substance. g was placed in the reactor, and the internal temperature of the reactor was maintained at 37 ° C. A solution of 15.1 mmol of n-butyllithium in cyclohexane was supplied to the reaction.

S 150826.doc -37· 201120073 In the reactor as a polymerization initiator. After the start of the polymerization, the temperature in the reactor began to rise due to the heat generated by the polymerization, and the temperature in the final reactor reached 70 °C. After completion of the polymerization reaction, 3.39 mmol of 4-, 4-bis[3-(dioxaxoxin)propyl]α Chen p well was added to the reactor, and the modification reaction was carried out at 69 ° C for 5 minutes. At this time, the molar ratio of the total amount of the methoxy group bonded to the decyl group in the added modifier to the amount of the n-butyl group added was 丨3 5 . After adding 2·1 g of an antioxidant (ΒΗΤ) to the polymer solution, the solvent was removed by steam stripping, and drying was performed by a dryer to obtain a styrene-butadiene copolymer containing a modified component (sample D. The result of knife analysis (sample I) was that the amount of ethylene in the bond was 26% by mass, and the amount of bonded butadiene was 74%. The viscosity of the polymer had a viscosity of 60. It was determined by using an infrared spectrophotometer. As a result, the amount of vinyl bond (丨, 2-bond amount) of the microstructure of the butadiene portion determined by the calculation by the Hampton method was 56%. The glass transition temperature was -23 °C.

The 372,000' number average molecular weight (Mn) is 31 ", 17. [Comparative Example 7]

43 it. A cyclohexane solution containing n-butyllithium 6.52 amide to maintain the internal temperature of the reactor at mm 〇 1 was supplied to the reverse 150826.doc -38·201120073 as a polymerization initiator. After the start of the polymerization, the temperature in the reactor began to rise due to the heat generated by the polymerization, and the temperature in the final reactor reached 71 °C. After the completion of the polymerization reaction, 4.35 mmol of 1-[3-(triethoxydecyl)propyl]-4-f-base was added to the reactor, and the modification reaction was carried out at 70 ° C for 5 minutes. After adding an antioxidant (ΒΗΤ) 2·1 g to the polymer solution, the solvent was removed by steaming KK', and drying treatment was performed by a dryer to obtain a stupid ethylene-butadiene copolymer containing a modified component (sample j). As a result of the analysis (Sample J), the amount of bonded styrene was 26% by mass, and the bond was butyl - 74% in dilute summer. The polymer has a Mona viscosity of 58. From the measurement results using an infrared spectrophotometer, the amount of vinyl bond (丨, 2• bond amount) of the microstructure of the butadiene portion determined by the Hampton method was 56%. The glass transition temperature is -23. (: The weight average molecular weight (Mw) in terms of polystyrene measured by GPC is 368,000, and the number average molecular weight (Mn) is 280,000, and 1^^/]^[11 is 丨31. [Example 12, Comparative Example 8 The sample obtained in Example 11 and Comparative Example 7 (the sample and the raw material rubber were blended as described below to obtain a rubber composition containing each raw material rubber. Modified conjugated diene system) Polymer (sample hj) ···································· 39)) : 20.0 parts by mass of decane coupling agent (manufactured by Evonik Degussa Co., Ltd., Si75): 2.0 parts by mass of S-RAE oil (manufactured by JX Nippon Mining & Energy Co., Ltd., JOMO Process NC140): 5.0 parts by mass zinc white: 3.0 Parts by mass stearic acid: 2.0 parts by mass of anti-aging agent (Ν-isopropyl-Ν'-phenyl-p-phenylenediamine): 1.0 part by mass of sulfur: 1.9 parts by mass of vulcanization accelerator (Ν-cyclohexyl-2- Benzothiazolylsulfinamide): 1.0 part by mass of vulcanization accelerator (diphenylphosphonium): 1.5 parts by mass 162.4 parts by mass of the rubber composition was kneaded by the same method as in Examples 6 to 10 and Comparative Examples 4 to 6. The physical properties of the rubber composition were carried out in the same manner as in Examples 6 to 10 and Comparative Examples 4 to 6. The measurement results of the physical properties are shown in Table 6. The results are shown by an index value, and Comparative Example 8 is set to "100". [Table 6] Example 12 Comparative Example 8 Styrene-butadiene copolymer IJ formulation Material Mona viscosity 64 71 vulcanized rubber physical tensile strength index 99 100 wear resistance index 101 100 0 ° C tan5 (strain 1%) index 103 100 50 ° Ctan5 (strain 3%) index 96 100 as shown in Table 6, It was confirmed that the modified conjugated diene polymer composition of Example 12 had a lower tan5 at a higher temperature than the composition of Comparative Example 8, and the magnetic hysteresis was 150826.doc -40·201120073, which was less expensive. The rotation resistance is high and the tanS at low temperature is high, and the wet skid resistance is excellent. Further, it is confirmed that the viscosity of the blended material is low, and the balance between the workability and the physical properties of the vulcanized rubber is excellent. Further, it is confirmed that the wear resistance and the tensile strength are also good. Confirmed by the above content, this implementation When the modified conjugated diene polymer is made into a vulcanized rubber, it has excellent balance between low hysteresis loss and wet skid resistance, and has practically sufficient wear resistance or fracture strength, and is excellent in workability. The application (4) is based on the patent application of the Japanese Patent Office (Japanese Patent Application) (Japanese Patent Application No. 2_23〇4ΐ2), the contents of which are incorporated herein by reference. [Industrial Applicability] π According to the method for producing a modified diene-based polymer of the present invention, the balance between low hysteresis loss and wet skid resistance is excellent when f-vulcanized rubber is prepared, and sufficient wear resistance is used. A conjugated diene-based polymer which is excellent in workability and processability, and which is excellent in workability, can be preferably used as a material for various members such as a tread industrial product. 150826.doc

Claims (1)

201120073 VII. Patent application scope: 1. A method for manufacturing a modified total diene polymer, comprising the following steps: a polymerization step of using an alkali metal compound or an alkaline earth metal compound as a polymerization initiator to conjugate a diene compound or a conjugated diene compound' is polymerized or copolymerized with an aromatic vinyl compound, thereby obtaining a copolydiene polymer having an active terminal; and a upgrading step 'which conjugates the modifier with the above The above-mentioned activity of the diene polymer is a terminal reaction having one or more heterocyclic structures containing two or more nitrogen atoms and a hydrocarbon, and two or more bonds are bonded thereto. A compound of the above alkyl alkoxy group. 2. The method for producing a modified conjugated diene polymer according to Item 1, wherein the modifying agent is a compound represented by the following formula (1): [Chemical Formula 1] R (R N (3 - m) (In the formula (1) 5, R1 to R4 are each independently, and represent an alkyl group having 1 to 20 carbon atoms or an aromatic (1) soil. R and R are each independently, and represent an alkylene group having a carbon number of 1 to 20, and R7 and R8 are knives. Independently, it does not represent a hydrocarbon group having 1 to 6 carbon atoms, and 2 adjacent N groups form a ring structure of 5 % or more, and the claws and n each independently represent 2 or 3). 3. The method for producing a modified conjugated diene polymer in the above modifier according to claim 1 or 2, wherein all of the decyl groups are bonded with 3 alkoxy groups. S 150826.doc 201120073 decane base. 4. The method for producing a modified conjugated diene polymer according to claim 2 or 2, wherein the total number of moles of the alkoxy group bonded to the alkylene group in the modifying agent is the polymerization initiator 5. The method of producing a modified conjugated diene polymer according to claim 1 or 2, wherein the polymerization step is a continuous one. 6. The method for producing a modified conjugated diene polymer according to claim 1 or 2, wherein the modified conjugated diene polymer is converted to polystyrene by gel permeation chromatography (Gpc) A modified conjugated diene polymer having an average molecular weight of 2 Å, 〇〇〇 〜 600, 〇〇〇〇7·, which is modified by a modification as claimed in any one of claims 1 to 6. A method of producing a diene polymer. A modified total light-thin polymer composition comprising: 20 parts by mass or more of the rubber component of the modified conjugated diene polymer of claim 7 and 1 part by mass, and dioxide矽-based inorganic filler 0 5~3 〇〇 parts by mass. 150826.doc 201120073 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: t 5 person 6 (RO)-Si-R--N, .N-R-Si——(OR2) (1) m l3 YL n ^ (3 — m) ^ (3 —n) 150826.doc -2-